Amphiphilic polymers for filtrate control

ABSTRACT

The present invention relates to the use of amphiphilic sequenced copolymers as an agent for controlling the filtrate in a fluid (F) injected under pressure into an underground formation, comprising—at least one chain (C) soluble in the fluid (F); and—at least one block (B) that is insoluble in the fluid (F).

This application is a U.S. national phase entry under 35 U.S.C. § 371 ofInternational Application No. PCT/EP2016/062439, filed on Jun. 2, 2016,which claims priority to French Application No. 1501147, filed on Jun.3, 2015. The entire contents of these applications are beingincorporated herein by this reference.

The present invention relates to the field of oil extraction. Morespecifically, it relates to agents providing an effect of control offluid loss in fluids injected under pressure into subterraneanformations.

In the field of oil extraction, numerous stages are carried out byinjecting fluids under pressure within subterranean formations. In thepresent description, the notion of “subterranean formation” isunderstood in its broadest sense and includes both a rock containinghydrocarbons, in particular oil, and the various rock layers traversedin order to access this oil-bearing rock and to ensure the extraction ofthe hydrocarbons. Within the meaning of the present description, thenotion of “rock” is used to denote any type of constituent material of asolid subterranean formation, whether or not the material constitutingit is strictly speaking a rock. Thus, in particular, the expression“oil-bearing rock” is employed here as synonym for “oil-bearingreservoir” and denotes any subterranean formation containinghydrocarbons, in particular oil, whatever the nature of the materialcontaining these hydrocarbons (rock or sand, for example).

Mention may in particular be made, among the fluids injected underpressure into subterranean formations, of the various fluids forcompletion and workover of the wells, in particular drilling fluids,whether they are used to access the oil-bearing rock or else to drillthe reservoir itself (“drill-in”), or else fracturing fluids, oralternatively completion fluids, control or workover fluids or annularfluids or packer fluids.

A specific case is that of oil cement grouts, which are employed for thecementing of the annulus of oil wells according to a method well-knownper se, for example described in Le Forage [Drilling] by J. P Nguyen(Editions Technip 1993). These oil cement grouts are injected underpressure within a metal casing introduced into the drilling hole of theoil wells, then rise again, under the effect of the pressure, via the“annulus” space located between the casing and the drilling hole, andthen set and harden in this annulus, thus ensuring the stability of thewell during drilling.

Within an oil extraction well, bringing the pressurized fluid intocontact with the subterranean formation (which generally exhibits a moreor less high porosity, or even cracks) results in an effect of “fluidloss”: the liquid present in the fluid has a tendency to penetrate intothe constituent rock of the subterranean formation, which can damage thewell, indeed even harm its integrity. When these fluids employed underpressure contain insoluble compounds (which is very often the case, inparticular for oil cement grouts or else drilling or fracturing fluids),the effect of fluid loss at the same time brings about risks of loss ofcontrol of the fluids injected an increase in the concentration ofinsoluble compounds of the fluid, which can result in an increase inviscosity, which affects the mobility of the fluid.

In the specific case of a cement grout, the fluid loss can in additionresult in aggregation or gelling of the grout, before the space of theannulus is filled with the grout, which can, inter alia, weaken thestructure of the well and harm its leaktightness.

For further details relating to the effect of fluid loss and itscementing effects, reference may in particular be made to WellCementing, E. B. Nelson (Elsevier, 1990).

For the purpose of inhibiting the phenomenon of fluid loss, a number ofadditives have been described which make it possible to limit (indeedeven in some cases completely prevent) the escape of the liquid presentin the fluid toward the rock with which it comes into contact. Theseadditives, known as “fluid loss control agents”, generally make itpossible to obtain, in parallel, an effect of control of the migrationof gases, namely isolation of the fluid with respect to the gasespresent in the rock (gases which it is advisable to prevent frompenetrating into the fluid, in particular in the case of cement grouts,these gases having a tendency to weaken the cement during setting).

Various fluid loss control agents of the abovementioned type have beenprovided, which include in particular cellulose derivatives (for examplehydroxyethylcellulose) or alternatively hydrophilic AMPS-basedcopolymers, such as those described, for example, in U.S. Pat. Nos.4,632,186 or 4,515,635. These additives are not always fully suitablefor providing, in practice, effective limitation of fluid loss. Inparticular, and this is especially the case in the field of oil cementgrouts, the presence of other additives can inhibit the effect of theagents employed for providing control of fluid loss. In particular, inthe presence of some dispersing agents or set retarders, theabovementioned fluid loss control agents generally experience adeterioration in their properties.

There is described, in WO 2015/049378, the use of a hydrophilic diblockpolymer as fluid loss control agent, namely a short block (A) bonded toa long block (B). The short block provides the effect of anchoring withthe cement particles and the block B provides the effect of localincrease in the viscosity of the fluid around the particles.

One aim of the present invention is to provide novel fluid loss controlagents for fluids injected under pressure into subterranean formations.

To this end, the present invention provides for the use, as agent forcontrolling fluid loss in a fluid (F) injected under pressure into asubterranean formation, of sequential copolymers (P) comprising

-   -   at least one chain (C) soluble in the fluid (F), typically        water-soluble; and    -   at least one block (B) insoluble in the fluid (F), typically        hydrophobic.

The polymer used according to the invention is an amphiphilic copolymer,in the sense that it comprises:

-   -   the chain (C) which is a chain soluble in the fluid (F),        typically having a solubility at 20° C. of greater than or equal        to 0.5% (5 000 ppm), preferably of greater than or equal to 1%,        in the fluid (F),    -   the block (B) which is a polymer sequence insoluble in the fluid        (F), typically having a solubility at 20° C. of less than or        equal to 0.1% (1000 ppm) in the fluid (F).

The block (B) can be:

-   -   external to the chain (C):    -   use may typically be made of diblock, triblock or multiblock        polymers where at least one of the blocks consists of the        chain (C) and at least one of the other blocks is the block (B);        or    -   incorporated in the chain (C):    -   in this case, the chain (C) is soluble overall but contains at        least one insoluble sequence. Preferably, the insoluble sequence        or sequences represent between 0.05 and 5% of the total weight        of the chain (C).

The control of the fluid loss carried out according to the invention isobtained in the context of an oil extraction and it makes it possible tolimit, indeed even completely inhibit, the escape of the fluid (F),typically water or an aqueous composition, into the subterraneanformation where the extraction is being carried out. This control of thefluid loss can in particular be obtained when the polymers of theinvention are employed with particles but control of the fluid loss canalso be obtained in the absence of particles. When the polymers areemployed with particles, they can be particles present within thesubterranean formation and/or particles injected within the subterraneanformation, typically in conjunction with the copolymers (such as, forexample, cement particles in the case of a fluid employed in cementing).

According to a specific embodiment, the chain (C) is of the typeobtained by micellar polymerization. In this case, the chain (C) issoluble overall and typically comprises a chain predominantly formed ofhydrophilic units interrupted at different points by a plurality ofhydrophobic sequences (B) of substantially identical size. According tothis embodiment, the polymer of the invention can consist of the chain(C) or else be a block copolymer where the chain (C) constitutes one ofthe blocks.

Micellar polymerization consists schematically in carrying out apolymerization of hydrophilic monomers in a hydrophilic mediumcomprising micelles including hydrophobic monomers. Examples of micellarpolymerization have in particular been described in U.S. Pat. No.4,432,881 or else in Polymer, Vol. 36, No. 16, pp. 3197-3211 (1996), towhich documents reference may be made for further details.

Use may typically be made, according to the invention, of a micellarpolymerization, where the following are copolymerized (typically via theradical route) within an aqueous dispersing medium (typically water or awater/alcohol mixture):

-   -   hydrophilic monomers in the dissolved or dispersed state in said        medium; and    -   hydrophobic monomers within surfactant micelles formed in said        medium by introducing this surfactant therein at a concentration        above its critical micelle concentration (cmc).

Preferably, the content of hydrophobic monomers corresponding to theratio of the weight of the hydrophobic monomers with respect to thetotal weight of the hydrophobic and hydrophilic monomers is greater thanor equal to 0.05%, preferably greater than 0.1%, indeed even greaterthan 0.2%, and less than or equal to 5%. Generally, the percentage ofthe hydrophobic units in the chain (C) is of the same order, typicallygreater than or equal to 0.05%, preferably greater than 0.1%, indeedeven greater than 0.2%, and less than or equal to 5%.

According to a specific embodiment, the hydrophobic monomers presentwithin surfactant micelles employed in micellar polymerization can bemonomers which, in themselves, have the property of forming micelleswithout needing to add additional surfactants (monomers referred to as“self-micellizable”). According to this specific embodiment, thesurfactant employed can be the self-micellizable hydrophobic monomeritself, employed without other surfactant, although the presence of suchan additional surfactant is not excluded. Thus, within the meaning ofthe present description, when mention is made of hydrophobic monomerswithin surfactant micelles, this notion encompasses both (i) hydrophobicmonomers present within surfactant micelles other than these monomersand (ii) monomers comprising at least one hydrophobic part or block andforming by themselves the micelles in aqueous medium. The twoabovementioned embodiments (i) and (ii) are compatible and can coexist(hydrophobic monomers within micelles formed by anotherself-micellizable monomer for example, or else micelles comprising acombination of surfactants and self-micellizable monomers).

In micellar polymerization, the hydrophobic monomers present in themicelles are said to be in “micellar solution”. The micellar solution towhich reference is made is a micro-heterogeneous system which isgenerally isotropic, optically transparent and thermodynamically stable.

It should be noted that a micellar solution of the type employed inmicellar polymerization should be distinguished from a microemulsion. Inparticular, in contrast to a microemulsion, a micellar solution isformed at any concentration exceeding the critical micelle concentrationof the surfactant employed, with the sole condition that the hydrophobicmonomer be soluble at least to a certain extent within the internalspace of the micelles. A micellar solution furthermore differs from anemulsion in the absence of homogeneous internal phase: the micellescontain a very small number of molecules (typically less than 1000,generally less than 500 and typically from 1 to 100, with most often 1to 50, monomers, and at most a few hundred surfactant molecules, when asurfactant is present) and the micellar solution generally has physicalproperties similar to those of the monomer-free surfactant micelles.Moreover, generally, a micellar solution is transparent with respect tovisible light, given the small size of the micelles, which does notresult in refraction phenomena, unlike the drops of an emulsion, whichrefract light and give it its characteristic cloudy or white appearance.

The micellar polymerization technique results in characteristicsequential polymers which each comprise several hydrophobic blocks ofsubstantially the same size and where this size can be controlled.Specifically, given the confinement of the hydrophobic monomers withinthe micelles, each of the hydrophobic blocks comprises substantially oneand the same defined number n_(H) of hydrophobic monomers, it beingpossible for this number n_(H) to be calculated as follows(Macromolecular Chem. Physics, 202, 8, 1384-1397, 2001):n _(H) =N _(agg)·[M _(H)]/([surfactant]−cmc)where:

-   N_(agg) is the aggregation number of the surfactant, which reflects    the surfactant number present in each micelle-   [M_(H)] is the molar concentration of hydrophobic monomer in the    medium-   [surfactant] is the molar concentration of surfactant in the medium    and-   cmc is the critical micelle (molar) concentration.

The micellar polymerization technique thus makes possible advantageouscontrol of the hydrophobic units introduced into the polymers formed,namely:

-   -   overall control of the molar fraction of hydrophobic units in        the polymer (by adjusting the ratio of the concentrations of the        two monomers); and    -   more specific control of the number of hydrophobic units present        in each of the hydrophobic blocks (by modifying the parameters        influencing the n_(H) defined above).

The chain (C) overall soluble in the fluid (F), which is obtained bymicellar polymerization, comprises:

-   -   a hydrophilic component, composed of the hydrophilic monomers,        which corresponds to a hydrophilic polymer chain which would        have a solubility typically of greater than or equal to 1% (10        000 ppm) at 20° C. if it were introduced alone into the fluid        (F),    -   a hydrophobic component, composed of the hydrophobic sequences,        each having a solubility typically of less than or equal to 0.1%        (1 000 ppm) at 20° C. in the fluid (F).

In many cases, the chain (C) can be described as a hydrophilic chainhaving the abovementioned solubility (at least 1%) to which pendanthydrophobic groups are grafted. In particular in this case, the chain(C) has overall a solubility at 20° C. in the fluid (F) which preferablyremains greater than or equal to 0.1%, indeed even 0.5%.

According to a specific embodiment, the chain (C) is of the typeobtained by a process comprising a stage (e) of micellar radicalpolymerization in which the following are brought into contact, withinan aqueous medium (M):

-   -   hydrophilic monomers, dissolved or dispersed in said aqueous        medium (M) (typically water or a water/alcohol mixture);    -   hydrophobic monomers in the form of a micellar solution, namely        a solution containing, in the dispersed state within the medium        (M), micelles comprising these hydrophobic monomers (it being        possible in particular for this dispersed state to be obtained        using at least one surfactant); and    -   at least one radical polymerization initiator, this initiator        typically being water-soluble or water-dispersible.

According to a preferred embodiment, the chain (C) is of the typeobtained by a process comprising a stage (E) of micellar radicalpolymerization in which the following are brought into contact, withinan aqueous medium (M):

-   -   hydrophilic monomers, dissolved or dispersed in said aqueous        medium (M) (typically water or a water/alcohol mixture);    -   hydrophobic monomers in the form of a micellar solution, namely        a solution containing, in the dispersed state within the medium        (M), micelles comprising these hydrophobic monomers (it being        possible in particular for this dispersed state to be obtained        using at least one surfactant);    -   at least one radical polymerization initiator, this initiator        typically being water-soluble or water-dispersible; and    -   at least one radical polymerization control agent.

Stage (E) is similar to the abovementioned stage (e) but employs anadditional control agent. This stage, known under the name of“controlled-nature micellar radical polymerization”, has in particularbeen described in WO 2013/060741. All the alternative forms described inthis document can be used here.

Within the meaning of the present description, the term “radicalpolymerization control agent” is understood to mean a compound which iscapable of extending the lifetime of the growing polymer chains in apolymerization reaction and of conferring, on the polymerization, aliving or controlled nature. This control agent is typically areversible transfer agent as employed in controlled radicalpolymerizations denoted under the terminology RAFT or MADIX, whichtypically employ a reversible addition-fragmentation transfer process,such as those described, for example, in WO 96/30421, WO 98/01478, WO99/35178, WO 98/58974, WO 00/75207, WO 01/42312, WO 99/35177, WO99/31144, FR 2 794 464 or WO 02/26836.

According to an advantageous embodiment, the radical polymerizationcontrol agent employed in stage (E) is a compound which comprises athiocarbonylthio—S(C═S)— group. Thus, for example, it can be a compoundwhich comprises a xanthate group (carrying—SC═S—O— functional groups),for example a xanthate. Other types of control agent can be envisaged(for example of the type of those employed in CRP or in ATRP).

According to a specific embodiment, the control agent employed in stage(E) can be a polymer chain resulting from a controlled radicalpolymerization and carrying a group which is capable of controlling aradical polymerization (polymer chain of “living” type, which is a typewell known per se). Thus, for example, the control agent can be apolymer chain (preferably hydrophilic or water-dispersible)functionalized at the chain end with a xanthate group or more generallycomprising an —SC═S— group, for example obtained according to the MADIXtechnology.

Alternatively, the control agent employed in stage (E) is anon-polymeric compound carrying a group which ensures the control of theradical polymerization, in particular a thiocarbonylthio —S(C═S)— group.

According to a specific alternative form, the radical polymerizationcontrol agent employed in stage (E) is a polymer, advantageously anoligomer, having a water-soluble or water-dispersible nature andcarrying a thiocarbonylthio —S(C═S)— group, for example a xanthate—SC═S—O— group. This polymer, which is capable of acting both as controlagent for the polymerization and as monomer in stage (E), is alsodenoted by “prepolymer” in the continuation of the description.Typically, this prepolymer is obtained by radical polymerization ofhydrophilic monomers in the presence of a control agent carrying athiocarbonylthio —S(C═S)— group, for example a xanthate. Thus, forexample, according to an advantageous embodiment which is illustrated atthe end of the present description, the control agent employed in stage(E) can advantageously be a prepolymer carrying a thiocarbonylthio—S(C═S)— group, for example a xanthate —SC═S—O— group, obtained onconclusion of a stage (E⁰) of controlled radical polymerization prior tostage (E). In this stage (E⁰), hydrophilic monomers, advantageouslyidentical to those employed in stage (E); a radical polymerizationinitiator and a control agent carrying a thiocarbonylthio —S(C═S)—group, for example a xanthate, can typically be brought into contact.

The use of the abovementioned stage (E⁰) prior to stage (E) makes itpossible, schematically, to hydrophilize a large number of controlagents carrying thiocarbonylthio functional groups (for examplexanthates, which are rather hydrophobic by nature), by converting themfrom prepolymers which are soluble or dispersible in the medium (M) ofstage (E). Preferably, a prepolymer synthesized in stage (E⁰) has ashort polymer chain, for example comprising a series of less than 50monomer units, indeed even less than 25 monomer units, for examplebetween 2 and 15 monomer units.

When stage (E) is employed, the polymers according to the inventioncomprise chains (C) which have a “controlled” structure, namely that allthe chains (C) present on the polymers have substantially the same sizeand the same structure. The chains (C) comprise in particular the blocks(B) substantially in the same number and proportion.

The specific polymer (P) employed in the context of the presentinvention, due to the presence of the hydrophobic sequences in ahydrophilic polymer chain, turns out to provide a control effect on thefluid which is particularly effective: without wishing to be committedto a theory, it appears that the hydrophobic units within a hydrophilicchain and/or different hydrophilic chains have a tendency to associatewith one another. In a way, a “plug” effect is thus obtained at theporosities of the rock, which makes it possible to limit, indeed even tocompletely block, the phenomenon of filtration.

In addition, it has been demonstrated that this effect of controllingthe filtrate was provided when the hydrophobic interactions betweenpolymers and between the polymer and the particles (p) are sufficientlystrong and numerous, in the case where the polymers are employed withthe particles, or when the hydrophobic interactions between polymers aresufficiently strong and numerous, in the case where the polymers areemployed without the particles.

For this, according to one embodiment of the invention, the number n_(H)is equal to or greater than 3, preferably greater than 4, for examplegreater than 6.

The number n_(H) is generally less than 30.

According to a preferred embodiment, the number n_(H) is between 6 and20 (limits included).

According to a first alternative form of the invention, the injectedfluid (F) comprises the polymer (P) but does not comprise solidparticles (p), and it encounters said particles (p) within thesubterranean formation subsequent to its injection. The associationbetween particles and polymers then takes place in situ. Such a fluidcan, for example, be injected during a drilling operation, and the rockcuttings formed during the drilling then perform the role of theparticles (p) in situ.

According to an alternative variant, the injected fluid (F) comprises,before the injection, at least a portion and generally all of theparticles (p) associated with the polymer (P), it being understood thatit can optionally encounter other particles (p) within the subterraneanformation.

Two forms can in particular be envisaged in this context:

-   -   form 1: the polymer (P) and the particles (p) are mixed during        the formulation of the fluid (F), on the site of operation or        upstream, typically by adding the particles (p), in the dry        state or optionally in the dispersed state, to a composition        comprising the polymer (P) in solution. According to this        alternative form, the fluid (F) can, for example, be an oil        cement grout, which is prepared by adding cement powder as        particles (p) to an aqueous composition comprising the        polymer (P) in solution.    -   form 2: the fluid (F) is manufactured, advantageously on the        site of operation, from a composition (premix) prepared upstream        (hereinafter denoted by the term “blend”) comprising the        polymer (P) and at least a portion of the particles (p),        generally within a dispersing liquid. In order to form the fluid        (F), this blend is mixed with the other constituents of the        fluid (F).

In the context of these forms 1 and 2, the polymer (P) incidentallyexhibits the not insignificant advantage of improving the dispersibilityand suspending of the particles (p). In some embodiments, the polymers(P) associated with the particles (p) can be employed mainly asdispersing and stabilizing agent for the dispersion of the particles(p), at the same time providing an effect of agent for control of fluidloss.

Various specific advantages and embodiments of the invention will now bedescribed in more detail.

The Fluid (F)

The term “fluid” is understood to mean, within the meaning of thedescription, any homogeneous or non-homogeneous medium comprising aliquid or viscous vector which optionally transports a liquid or gelleddispersed phase and/or solid particles, said medium being overallpumpable by means of the devices for injection under pressure used inthe application under consideration.

The term “liquid or viscous vector” of the fluid (F) is understood tomean the fluid itself, or else the solvent, in the case where the fluidcomprises dissolved compounds, and/or the continuous phase, in the casewhere the fluid comprises dispersed elements (droplets of liquid orgelled dispersed phase, solid particles, and the like).

According to a highly suitable embodiment, the fluid (F) is an aqueousfluid. The term “aqueous” is understood here to mean that the fluidcomprises water as liquid or viscous vector, either as sole constituentof the liquid or viscous vector or in combination with otherwater-soluble solvents.

In the case of the presence of solvents other than water in the liquidor viscous vector of the fluid (F), the water advantageously remains thepredominant solvent within the liquid or viscous vector, advantageouslypresent in a proportion of at least 50% by weight, indeed even of atleast 75% by weight, with respect to the total weight of the solvents inthe liquid or viscous vector.

The Particles (p)

The notion of “particle” within the meaning under which it is employedin the present description is not confined to that of individualparticles. It more generally denotes solid entities which can bedispersed within a fluid, in the form of objects (individual particles,aggregates, and the like) for which all the dimensions are less than 5mm, preferably less than 2 mm, for example less than 1 mm.

The particles (p) according to the invention can be chosen from: calciumcarbonate or cement, silica or sand, clay, carbon black and/or theirmixtures.

According to a specific embodiment of the invention, the particles (p)are calcium carbonate or cement particles.

The Polymers (P)

The Hydrophilic Monomers

The chain (C) can typically comprise monomers chosen from:

-   -   carboxylic acids which are ethylenically unsaturated, sulfonic        acids and phosphonic acids, and/or its derivatives, such as        acrylic acid (AA), methacrylic acid, ethacrylic acid,        α-chloroacrylic acid, crotonic acid, maleic acid, maleic        anhydride, itaconic acid, citraconic acid, mesaconic acid,        glutaconic acid, aconitic acid, fumaric acid, monoethylenically        unsaturated dicarboxylic acid monoesters comprising from 1 to 3        and preferably from 1 to 2 carbon atoms, for example monomethyl        maleate, vinylsulfonic acid, (meth)allylsulfonic acid,        sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl        acrylate, sulfopropyl methacrylate, 1-allyloxy-2-hydroylpropyl        sulfonate, 2-hydroxy-3-acryloyloxypropylsulfonic acid,        2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic        acids, 2-acrylamido-2-methylpropanesulfonic acid,        vinylphosphonic acid, α-methylvinylphosphonic acid and        allylphosphonic acid;    -   esters of α,β-ethylenically unsaturated mono- and dicarboxylic        acids with C₂-C₃ alkanediols, for example 2-hydroxyethyl        acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl        ethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl        methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl        methacrylate and polyalkylene glycol (meth)acrylates;    -   α,β-ethylenically unsaturated monocarboxylic acid amides and        their N-alkyl and N,N-dialkyl derivatives, such as acrylamide,        methacrylamide, N-methyl(meth)acrylamide,        N-ethyl(meth)acrylamide, N-isopropyl(meth)-acrylamide,        N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide,        morpholinyl(meth)acrylamide, and methylolacrylamide (acrylamide        and N,N-dimethyl(meth)acrylamide prove to be in particular        advantageous);    -   N-vinyllactams and its derivatives, for example        N-vinylpyrrolidone or N-vinylpiperidone;    -   open-chain N-vinylamide compounds, for example N-vinylformamide,        N-vinyl-N-methylformamide, N-vinylacetamide,        N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide,        N-vinylpropionamide, N-vinyl-N-methylpropionamide and        N-vinylbutyramide;    -   esters of α,β-ethylenically unsaturated mono- and dicarboxylic        acids with aminoalcohols, for example N,N-dimethylaminomethyl        (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate,        N,N-diethylaminoethyl acrylate and N,N-dimethylaminopropyl        (meth)acrylate;    -   amides of α,β-ethylenically unsaturated mono- and dicarboxylic        acids with diamines comprising at least one primary or secondary        amino group, such as N-[2-(dimethylamino)ethyl]acrylamide,        N-[2-(dimethylamino)ethyl]-methacrylamide,        N-[3-(dimethylamino)propyl]acrylamide,        N-[3-(dimethylamino)-propyl]methacrylamide,        N-[4-(dimethylamino)butyl]acrylamide and        N-[4-(dimethylamino)butyl]methacrylamide;    -   N-diallylamines, N,N-diallyl-N-alkylamines, their acid addition        salts and their quaternization products, the alkyl employed here        preferably being C₁-C₃ alkyl;    -   N,N-diallyl-N-methylamine and N,N-diallyl-N,N-dimethylammonium        compounds, for example the chlorides and bromides;    -   nitrogenous heterocycles substituted with vinyl and allyl, for        example N-vinylimidazole, N-vinyl-2-methylimidazole,        heteroaromatic compounds substituted with vinyl and allyl, for        example 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and        their salts;    -   sulfobetaines; and    -   the salts of the abovementioned monomers;    -   the mixtures and combinations of two or more of the monomers        and/or their salts mentioned above.

According to a specific embodiment, these monomers can in particularcomprise acrylic acid (AA).

According to another embodiment, the hydrophilic monomers of the chain(C) comprise (and typically consist of) (meth)acrylamide monomers, ormore generally (meth)acrylamido monomers, including:

-   acrylamido monomers, namely acrylamide (Am), dimethylacrylamide    (DMA), its sulfonate derivative, in particular    acrylamidomethylpropanesulfonic acids (AMPS);-   the quaternary ammonium APTAC and    sulfopropyldimethylammoniopropylacrylamide;-   methacrylamido monomers, such as    sulfopropyldimethylammoniopropylmethacrylamide (SPP) or    sulfohydroxypropyldimethylammoniopropylmethacrylamide.

According to a specific embodiment, the hydrophilic monomers of thechain (C) are acrylamides. An acrylamide is preferably an acrylamidewhich is not stabilized with copper.

According to a specific embodiment, the hydrophilic monomers of thechain (C) are chosen from acrylamides, dimethylacrylamides (DMA),acrylamidomethylpropanesulfonic acids (AMPS), acrylic acids (AA), theirsalts and their mixtures.

According to a specific embodiment, the hydrophilic monomers of thechain (C) can typically have a polymerizable functional group ofacrylamido type and a side chain composed of ethylene oxide or propyleneoxide strings, or else based on N-isopropylacrylamide orN-vinylcaprolactam.

Hydrophobic Monomers

Mention may in particular be made, as nonlimiting examples ofhydrophobic monomers constituting the insoluble blocks which can be usedaccording to the invention, of:

-   -   vinylaromatic monomers, such as styrene, α-methylstyrene,        para-chloromethylstyrene, vinyltoluene, 2-methylstyrene,        4-methylstyrene, 2-(n-butyl)styrene, 4-(n-decyl)styrene or        tert-butylstyrene;        -   halogenated vinyl compounds, such as vinyl or vinylidene            halides, for example vinyl or vinylidene chlorides or            fluorides, corresponding to the formula            R_(b)R_(c)C═CX¹X²,        -    where: X¹=F or Cl            -   X²=H, F or Cl            -   each one of R_(b) and R_(c), represents, independently:                -   H, Cl, F; or                -   an alkyl group, preferably chlorinated and/or                    fluorinated, more advantageously perchlorinated or                    perfluorinated;        -   esters of α,β-ethylenically unsaturated mono- or            dicarboxylic acid with C₂-C₃₀ alkanols, for example methyl            ethacrylate, ethyl (meth)acrylate, ethyl ethacrylate,            n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl            (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl            (meth)acrylate, tert-butyl ethacrylate, n-hexyl            (meth)acrylate, n-heptyl (meth)acrylate, n-octyl            (meth)acrylate, 1,1,3,3-tetramethylbutyl (meth)acrylate,            ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl            (meth)acrylate, n-undecyl (meth)acrylate, tridecyl            (meth)acrylate, myristyl (meth)acrylate, pentadecyl            (meth)acrylate, palmityl (meth)acrylate, heptadecyl            (meth)acrylate, nonadecyl (meth)acrylate, arachidyl            (meth)acrylate, behenyl (meth)acrylate, lignoceryl            (meth)acrylate, cerotinyl (meth)acrylate, melissinyl            (meth)acrylate, palmitoleoyl (meth)acrylate, oleyl            (meth)acrylate, linoleyl (meth)acrylate, linolenyl            (meth)acrylate, stearyl (meth)acrylate, lauryl            (meth)acrylate and their mixtures;        -   esters of vinyl or allyl alcohol with C₁-C₃₀ monocarboxylic            acids, for example vinyl formate, vinyl acetate, vinyl            propionate, vinyl butyrate, vinyl laurate, vinyl stearate,            vinyl propionate, vinyl versatate and their mixtures;        -   ethylenically unsaturated nitriles, such as acrylonitrile,            methacrylonitrile and their mixtures;        -   esters of α,β-ethylenically unsaturated mono- and            dicarboxylic acids with C₃-C₃₀ alkanediols, for example            3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate,            4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate,            6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate,            3-hydroxy-2-ethylhexyl acrylate and 3-hydroxy-2-ethylhexyl            methacrylate, and the like;        -   primary amides of α,β-ethylenically unsaturated mono- and            dicarboxylic acids and N-alkyl and N,N-dialkyl derivatives,            such as N-propyl(meth)acrylamide,            N-(n-butyl)(meth)acrylamide, N-(tert-butyl)(meth)acrylamide,            N-(n-octyl)(meth)-acrylamide,            N-(1,1,3,3-tetramethylbutyl)(meth)acrylamide,            N-ethylhexyl(meth)-acrylamide, N-(n-nonyl)(meth)acrylamide,            N-(n-decyl)(meth)acrylamide, N-(n-undecyl)(meth)acrylamide,            N-tridecyl(meth)acrylamide, N-myristyl(meth)-acrylamide,            N-pentadecyl(meth)acrylamide, N-palmityl(meth)acrylamide,            N-heptadecyl(meth)acrylamide, N-nonadecyl(meth)acrylamide,            N-arachidyl-(meth)acrylamide, N-behenyl(meth)acrylamide,            N-lignoceryl(meth)acrylamide, N-cerotinyl(meth)acrylamide,            N-melissinyl(meth)acrylamide,            N-palmitoleoyl-(meth)acrylamide, N-oleyl(meth)acrylamide,            N-linoleyl(meth)acrylamide, N-linolenyl(meth)acrylamide,            N-stearyl(meth)acrylamide and N-lauryl(meth)-acrylamide;        -   N-vinyllactams and its derivatives, such as            N-vinyl-5-ethyl-2-pyrrolidone,            N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone,            N-vinyl-7-methyl-2-caprolactam and            N-vinyl-7-ethyl-2-caprolactam, and the like;        -   esters of α,β-ethylenically unsaturated mono- and            dicarboxylic acids with aminoalcohols, for example            N,N-dimethylaminocyclohexyl (meth)acrylate;        -   amides of α,β-ethylenically unsaturated mono- and            dicarboxylic acids with diamines comprising at least one            primary or secondary amino group, for example            N-[4-(dimethylamino)butyl]acrylamide,            N-[4-(dimethylamino)butyl]-methacrylamide,            N-[2-(dimethylamino)ethyl]acrylamide,            N-[4-(dimethyl-amino)cyclohexyl]acrylamide,            N-[4-(dimethylamino)cyclohexyl]methacrylamide, and the like;            and        -   monoolefins (C₂-C₈) and nonaromatic hydrocarbons comprising            at least two conjugated double bonds, for example ethylene,            propylene, isobutylene, isoprene, butadiene, and the like.

According to a preferred embodiment, the hydrophobic monomers employedaccording to the invention can be chosen from:

-   -   C₁-C₃₀ alkyl and preferably C₄-C₂₂ alkyl α,β-unsaturated esters,        in particular alkyl acrylates and methacrylates, such as methyl,        ethyl, butyl, 2-ethylhexyl, isooctyl, lauryl, isodecyl or        stearyl acrylates and methacrylates (lauryl methacrylate in        particular proves to be especially advantageous);    -   C₁-C₃₀ alkyl and preferably C₄-C₂₂ alkyl α,β-unsaturated amides,        in particular alkylacrylamides and alkylmethacrylamides, such as        methyl-, ethyl-, butyl-, 2-ethylhexyl-, isooctyl-, lauryl-,        isodecyl- or stearylacrylamide or -methacrylamide        (laurylmethacrylamide in particular proves to be especially        advantageous);    -   vinyl or allyl alcohol esters of saturated carboxylic acids,        such as vinyl or allyl acetate, propionate, versatate or        stearate;    -   α,β-unsaturated nitriles comprising from 3 to 12 carbon atoms,        such as acrylonitrile or methacrylonitrile;    -   α-olefins and conjugated dienes;    -   vinylaromatic monomers, such as styrene, α-methylstyrene,        para-chloromethylstyrene, vinyltoluene, 2-methylstyrene,        4-methylstyrene, 2-(n-butyl)styrene, 4-(n-decyl)styrene or        tert-butylstyrene;    -   the mixtures and combinations of two or more of the        abovementioned monomers.

According to an advantageous embodiment, in particular when the fluid(F) is a fracturing fluid, use may be made of hydrophobic monomers whichbond feebly to the chain (C). This makes it possible, if necessary, toremove the polymers introduced within the subterranean formation (inview of their amphiphilic nature, the polymers of the inventiongenerally have a self-associative nature and tend to form gels which aredifficult to remove; under the effect in particular of the temperatureand/or the pH, it is possible to cleave the hydrophobic monomers if theyare not bonded excessively strongly to the polymer, which makes possibleremoval from the fluid). Hydrophobic monomers suited to this embodimentare in particular the abovementioned esters.

It should be noted that, when other monomers are used, removal from thefluids is still possible by a technique known per se, where “breakers”,such as oxidizing agents, are added. The preceding embodiment makes itpossible to dispense with the use of such “breakers”, which is reflectedin particular in terms of decrease in cost.

According to a specific embodiment, the synthesized polymers of theinvention can exhibit a molecular weight of greater than 600 000 g/mol,preferably of greater than 1 000 000 g/mol, indeed even ranging up to 2000 000.

According to a specific embodiment, the polymers can exhibit a molecularweight of greater than or equal to 2 000 000 g/mol, for example between2 000 000 and 3 000 000 g/mol, indeed even ranging up to 4 000 000g/mol.

The Radical Polymerization Control Agent

The control agent employed in stage (E) or, if appropriate, in stage(E⁰) of the process of the invention is advantageously a compoundcarrying a thiocarbonylthio —S(C═S)— group. According to a specificembodiment, the control agent can carry several thiocarbonylthio groups.It can optionally be a polymer chain carrying such a group.

Thus, this control agent can, for example, correspond to the formula (A)below:

in which:

-   -   Z represents:        -   a hydrogen atom,        -   a chlorine atom,        -   an optionally substituted alkyl or optionally substituted            aryl radical,        -   an optionally substituted heterocycle,        -   an optionally substituted alkylthio radical,        -   an optionally substituted arylthio radical,        -   an optionally substituted alkoxy radical,        -   an optionally substituted aryloxy radical,        -   an optionally substituted amino radical,        -   an optionally substituted hydrazine radical,        -   an optionally substituted alkoxycarbonyl radical,        -   an optionally substituted aryloxycarbonyl radical,        -   an optionally substituted acyloxy or carboxyl radical,        -   an optionally substituted aroyloxy radical,        -   an optionally substituted carbamoyl radical,        -   a cyano radical,        -   a dialkyl- or diarylphosphonato radical,        -   a dialkyl-phosphinato or diaryl-phosphinato radical, or        -   a polymer chain,            and    -   R₁ represents:        -   an optionally substituted alkyl, acyl, aryl, aralkyl,            alkenyl or alkynyl group,        -   a saturated or unsaturated, aromatic, optionally substituted            carbocycle or heterocycle, or        -   a polymer chain, which is preferably hydrophilic or            water-dispersible when the agent is employed in stage (E).

The R₁ or Z groups, when they are substituted, can be substituted byoptionally substituted phenyl groups, optionally substituted aromaticgroups, saturated or unsaturated carbocycles, saturated or unsaturatedheterocycles, or groups selected from the following: alkoxycarbonyl oraryloxycarbonyl (—COOR), carboxyl (—COOH), acyloxy (—O₂CR), carbamoyl(—CONR₂), cyano (—CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl,arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino,guanidimo, hydroxyl (—OH), amino (—NR₂), halogen, perfluoroalkylC_(n)F_(2n+1), allyl, epoxy, alkoxy (—OR), S-alkyl, S-aryl, groupsexhibiting a hydrophilic or ionic nature, such as alkali metal salts ofcarboxylic acids, alkali metal salts of sulfonic acids, polyalkyleneoxide (PEO, PPO) chains, cationic substituents (quaternary ammoniumsalts), R representing an alkyl or aryl group, or a polymer chain.

For the control agents of formula (A) employed in stage (E), it isgenerally preferred for the R₁ group to be of hydrophilic nature.Advantageously, it is a water-soluble or water-dispersible polymerchain.

The R₁ group can alternatively be amphiphilic, namely exhibit both ahydrophilic and a lipophilic nature. It is preferable for R₁ not to behydrophobic.

As regards the control agents of formula (A) employed in stage (E⁰), R₁can typically be a substituted or unsubstituted, preferably substituted,alkyl group. A control agent of formula (A) employed in stage (E⁰) cannevertheless comprise other types of R₁ groups, in particular a ring ora polymer chain.

The optionally substituted alkyl, acyl, aryl, aralkyl or alkynyl groupsgenerally exhibit from 1 to 20 carbon atoms, preferably from 1 to 12 andmore preferably from 1 to 9 carbon atoms. They can be linear orbranched. They can also be substituted by oxygen atoms, in particular inthe form of esters, sulfur atoms or nitrogen atoms.

Mention may in particular be made, among the alkyl radicals, of themethyl, ethyl, propyl, butyl, pentyl, isopropyl, tert-butyl, pentyl,hexyl, octyl, decyl or dodecyl radical.

The alkyne groups are radicals generally of 2 to 10 carbon atoms; theyexhibit at least one acetylenic unsaturation, such as the acetylenylradical.

The acyl group is a radical generally exhibiting from 1 to 20 carbonatoms with a carbonyl group.

Mention may in particular be made, among the aryl radicals, of thephenyl radical, which is optionally substituted, in particular by anitro or hydroxyl functional group.

Mention may in particular be made, among the aralkyl radicals, of thebenzyl or phenethyl radical, which is optionally substituted, inparticular by a nitro or hydroxyl functional group.

When R₁ or Z is a polymer chain, this polymer chain can result from aradical or ionic polymerization or from a polycondensation.

Advantageously, use is made, as control agent for stage (E) and also forstage (E⁰), if appropriate, of compounds carrying a xanthate —S(C═S)O—,trithiocarbonate, dithiocarbamate or dithiocarbazate functional group,for example carrying an O-ethyl xanthate functional group of formula—S(C═S)OCH₂CH₃.

When stage (E⁰) is carried out, it is in particular advantageous toemploy, as control agents in this stage, a compound chosen fromxanthates, trithiocarbonates, dithiocarbamates and dithiocarbazates.Xanthates prove to be very particularly advantageous, in particularthose carrying an O-ethyl xanthate —S(C═S)OCH₂CH₃ functional group, suchas O-ethyl S-(1-(methoxycarbonyl)ethyl) xanthate(CH₃CH(CO₂CH₃))S(C═S)OEt. Another possible control agent in stage (E⁰)is dibenzyl trithiocarbonate of formula PhCH₂S(C═S)SCH₂Ph (wherePh=phenyl).

The living prepolymers obtained in step (E⁰) by using the abovementionedcontrol agents prove to be particularly advantageous for carrying outstage (E).

Initiation and Implementation of the Radical Polymerizations of Stages(E) and (E⁰)

When it is employed in stage (E), the radical polymerization initiatoris preferably water-soluble or water-dispersible. Apart from thispreferential condition, any radical polymerization initiator (source offree radicals) known per se and suited to the conditions chosen forthese stages can be employed in stage (E) and stage (E⁰) of the processof the invention.

Thus, the radical polymerization initiator employed according to theinvention can, for example, be chosen from the initiators conventionallyused in radical polymerization. It can, for example, be one of thefollowing initiators:

-   -   hydrogen peroxides, such as: tert-butyl hydroperoxide, cumene        hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate,        t-butyl peroxyoctoate, t-butyl peroxyneodecanoate, t-butyl        peroxyisobutyrate, lauroyl peroxide, t-amyl peroxypivalate,        t-butyl peroxypivalate, dicumyl peroxide, benzoyl peroxide,        potassium persulfate or ammonium persulfate,    -   azo compounds, such as: 2,2′-azobis(isobutyronitrile),        2,2′-azobis(2-butanenitrile), 4,4′-azobis(4-pentanoic acid),        1,1′-azobis(cyclohexanecarbonitrile),        2-(t-butylazo)-2-cyanopropane,        2,2′-azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)-2-hydroxyethyl]-propionamide,        2,2′-azobis(2-methyl-N-hydroxyethyl]propionamide,        2,2′-azobis(N,N′-dimethyleneisobutyramidine)dichloride,        2,2′-azobis(2-amidinopropane)dichloride,        2,2′-azobis(N,N′-dimethyleneisobutyramide),        2,2′-azobis(2-methyl-N-[1,1-bis(hydroxy-methyl)-2-hydroxyethyl]propionamide),        2,2′-azobis(2-methyl-N-[1,1-bis(hydroxy-methyl)ethyl]propionamide),        2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] or        2,2′-azobis(isobutyramide)dihydrate,    -   redox systems comprising combinations, such as:    -   mixtures of hydrogen peroxide, alkyl peroxide, peresters,        percarbonates and the like and any iron salt, titanous salt,        zinc formaldehyde sulfoxylate or sodium formaldehyde        sulfoxylate, and reducing sugars,    -   alkali metal or ammonium persulfates, perborates or perchlorates        in combination with an alkali metal bisulfite, such as sodium        metabisulfite, and reducing sugars, and    -   alkali metal persulfates in combination with an arylphosphinic        acid, such as benzenephosphonic acid and the like, and reducing        sugars.

Typically, the amount of initiator to be used is preferably determinedso that the amount of radicals generated is at most 50 mol % andpreferably at most 20 mol %, with respect to the amount of control ortransfer agent.

Very particularly in stage (E), it generally proves to be advantageousto use a radical initiator of redox type, which exhibits, inter alia,the advantage of not requiring heating of the reaction medium (nothermal initiation), and the inventors of which have in addition nowdiscovered that it proves to be suitable for the micellar polymerizationof stage (E).

Thus, the radical polymerization initiator employed in stage (E) cantypically be a redox initiator, typically not requiring heating for itsthermal initiation. It is typically a mixture of at least one oxidizingagent with at least one reducing agent.

The oxidizing agent present in this redox system is preferably awater-soluble agent. This oxidizing agent can, for example, be chosenfrom peroxides, such as: hydrogen peroxide, tert-butyl hydroperoxide,cumene hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate,t-butyl peroxyoctoate, t-butyl peroxyneodecanoate, t-butylperoxyisobutyrate, lauroyl peroxide, t-amyl peroxypivalate, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, sodium persulfate,potassium persulfate, ammonium persulfate or also potassium bromate.

The reducing agent present in the redox system is also preferably awater-soluble agent. This reducing agent can typically be chosen fromsodium formaldehyde sulfoxylate (in particular in its dihydrate form,known under the name Rongalit, or in the form of an anhydride), ascorbicacid, erythorbic acid, sulfites, bisulfites or metasulfites (inparticular alkali metal sulfites, bisulfites or metasulfites),nitrilotrispropionamides, and tertiary amines and ethanolamines (whichare preferably water-soluble).

Possible redox systems comprise combinations, such as:

-   -   mixtures of water-soluble persulfates with water-soluble        tertiary amines,    -   mixtures of water-soluble bromates (for example, alkali metal        bromates) with water-soluble sulfites (for example, alkali metal        sulfites),    -   mixtures of hydrogen peroxide, alkyl peroxide, peresters,        percarbonates and the like and any iron salt, titanous salt,        zinc formaldehyde sulfoxylate or sodium formaldehyde        sulfoxylate, and reducing sugars,    -   alkali metal or ammonium persulfates, perborates or perchlorates        in combination with an alkali metal bisulfite, such as sodium        metabisulfite, and reducing sugars, and    -   alkali metal persulfates in combination with an arylphosphinic        acid, such as benzenephosphonic acid and the like, and reducing        sugars.

An advantageous redox system comprises (and preferably consists of) thecombination of ammonium persulfate and sodium formaldehyde sulfoxylate.

Generally, and in particular in the case of the use of a redox system ofthe ammonium persulfate/sodium formaldehyde sulfoxylate type, it provesto be preferable for the reaction medium of stage (E) to be devoid ofcopper. In the case of the presence of copper, it is generally desirableto add a copper-complexing agent, such as EDTA, in an amount capable ofmasking its presence.

Whatever the nature of the initiator employed, the radicalpolymerization of stage) (E⁰) can be carried out in any appropriatephysical form, for example in solution in water or in a solvent, forexample an alcohol or THF, in emulsion in water (“latex” process) or inbulk, if appropriate while controlling the temperature and/or the pH inorder to render entities liquid and/or soluble or insoluble.

After carrying out stage (E), given the specific use of a control agent,polymers functionalized with transfer groups (living polymers) areobtained. This living character makes it possible, if desired, to employthese polymers in a subsequent polymerization reaction, according to atechnique well known per se. Alternatively, if required, it is possibleto deactivate or to destroy the transfer groups, for example byhydrolysis, ozonolysis or reaction with amines, according to means knownper se. Thus, according to a specific embodiment, the process of theinvention can comprise, after stage (E), a stage (E1) of hydrolysis, ofozonolysis or of reaction with amines which is capable of deactivatingand/or destroying all or a portion of the transfer groups present on thepolymer prepared in stage (E).

Surfactants

Use may be made, in order to prepare the micellar solution of thehydrophobic monomers which are employed in stage (E), of any suitablesurfactant in a nonlimiting manner; use may be made, for example, of thesurfactants chosen from the following list:

-   -   The anionic surfactants can be chosen from:    -   alkyl ester sulfonates, for example of formula        R—CH(SO₃M)-CH₂COOR′, or alkyl ester sulfates, for example of        formula R—CH(OSO₃M)-CH₂COOR′, where R represents a C₈-C₂₀ and        preferably C₁₀-C₁₆ alkyl radical, R′ represents a C₁-C₆ and        preferably C₁-C₃ alkyl radical and M represents an alkali metal        cation, for example the sodium cation, or the ammonium cation.        Mention may very particularly be made of methyl ester        sulfonates, the R radical of which is a C₁₄-C₁₆ radical;    -   alkylbenzenesulfonates, more particularly C₉-C₂₀        alkylbenzenesulfonates, primary or secondary alkylsulfonates, in        particular C₈-C₂₂ alkylsulfonates, or alkylglycerolsulfonates;    -   alkyl sulfates, for example of formula ROSO₃M, where R        represents a C₁₀-C₂₄ and preferably C₁₂-C₂₀ alkyl or        hydroxyalkyl radical and M represents a cation with the same        definition as above;    -   alkyl ether sulfates, for example of formula RO(OA)_(n)SO₃M,        where R represents a C₁₀-C₂₄ and preferably C₁₂-C₂₀ alkyl or        hydroxyalkyl radical, OA represents an ethoxylated and/or        propoxylated group, M represents a cation with the same        definition as above and n generally varies from 1 to 4, such as,        for example, lauryl ether sulfate with n=2;    -   alkylamide sulfates, for example of formula RCONHR′OSO₃M, where        R represents a C₂-C₂₂ and preferably C₆-C₂₀ alkyl radical, R′        represents a C₂-C₃ alkyl radical and M represents a cation with        the same definition as above, and also their polyalkoxylated        (ethoxylated and/or propoxylated) derivatives (alkylamide ether        sulfates);    -   salts of saturated or unsaturated fatty acids, for example such        as C₅-C₂₄ and preferably C₁₄-C₂₀ acids, and of an alkaline earth        metal cation, N-acyl-N-alkyltaurates, alkylisethionates,        alkylsuccinamates and alkyl sulfosuccinates, alkylglutamates,        monoesters or diesters of sulfosuccinates, N-acylsarcosinates or        polyethoxycarboxylates;    -   monoester and diester phosphates, for example having the        following formula: (RO)_(x)—P(═O)(OM)_(x), where R represents an        optionally polyalkoxylated alkyl, alkylaryl, arylalkyl or aryl        radical, x and x′ are equal to 1 or 2, provided that the sum of        x and x′ is equal to 3, and M represents an alkaline earth metal        cation;    -   The nonionic surfactants can be chosen from:    -   alkoxylated fatty alcohols, for example laureth-2, laureth-4,        laureth-7 or oleth-20, alkoxylated triglycerides, alkoxylated        fatty acids, alkoxylated sorbitan esters, alkoxylated fatty        amines, alkoxylated di(1-phenylethyl)phenols, alkoxylated        tri(1-phenylethyl)phenols, alkoxylated alkylphenols, the        products resulting from the condensation of ethylene oxide with        a hydrophobic compound resulting from the condensation of        propylene oxide with propylene glycol, such as the Pluronic        products sold by BASF, the products resulting from the        condensation of ethylene oxide the compound resulting from the        condensation of propylene oxide with ethylenediamine, such as        the Tetronic products sold by BASF, alkylpolyglycosides, such as        those described in U.S. Pat. No. 4,565,647, or alkylglucosides,        or fatty acid amides, for example C₅-C₂₀ fatty acid amides, in        particular fatty acid monoalkanolamides, for example cocamide        MEA or cocamide MIPA;    -   The amphoteric surfactants (true amphoteric entities comprising        an ionic group and a potentially ionic group of opposite charge,        or zwitterionic entities simultaneously comprising two opposite        charges) can be:    -   betaines generally, in particular carboxybetaines, for example        lauryl betaine (Mirataine BB from Rhodia) or octyl betaine or        coco betaine (Mirataine BB-FLA from Rhodia); amidoalkyl        betaines, such as cocamidopropyl betaine (CAPB) (Mirataine BDJ        from Rhodia or Mirataine BET C-30 from Rhodia);    -   sulfobetaines or sultaines, such as cocamidopropyl        hydroxysultaine (Mirataine CBS from Rhodia);    -   alkylamphoacetates and alkylamphodiacetates, such as, for        example, comprising a cocoyl or lauryl chain (Miranol C2M Conc.        NP, C32, L32 in particular, from Rhodia);    -   alkylamphopropionates or alkylamphodipropionates (Miranol C2M        SF);    -   alkyl amphohydroxypropyl sultaines (Miranol CS);    -   alkylamine oxides, for example lauramine oxide (INCI);    -   The cationic surfactants can be optionally polyethoxylated        primary, secondary or tertiary fatty amine salts, quaternary        ammonium salts, such as tetraalkylammonium,        alkylamidoalkylammonium, trialkylbenzylammonium,        trialkylhydroxyalkylammonium or alkylpyridinium chlorides or        bromides, imidazoline derivatives or amine oxides having a        cationic nature. An example of a cationic surfactant is        cetrimonium chloride or bromide (INCI);    -   the surfactants employed according to the present invention can        be block copolymers comprising at least one hydrophilic block        and at least one hydrophobic block different from the        hydrophilic block, which are advantageously obtained according        to a polymerization process where:        -   (a₀) at least one hydrophilic (respectively hydrophobic)            monomer, at least one source of free radicals and at least            one radical polymerization control agent of the —S(C═S)—            type are brought together within an aqueous phase;        -   (a₁) the polymer obtained on conclusion of stage (a₀) is            brought into contact with at least one hydrophobic            (respectively hydrophilic) monomer different from the            monomer employed in stage (a₀) and at least one source of            free radicals; via which a diblock copolymer is obtained.

Polymers of the triblock type, or comprising more blocks, can optionallybe obtained by carrying out, after stage (a₁), a stage (a₂) in which thepolymer obtained on conclusion of stage (a₁) is brought into contactwith at least one monomer different from the monomer employed in stage(a₁) and at least one source of free radicals; and more generally bycarrying out (n+1) stages of the type of the abovementioned stages (a₁)and (a₂) and n is an integer typically ranging from 1 to 3, where, ineach stage (a_(n)), with the polymer obtained on conclusion of stage(a_(n-1)) is brought into contact with at least one monomer differentfrom the monomer employed in stage (a_(n-1)) and at least one source offree radicals. Use may be made, for example, according to the invention,of the copolymers of the type which are described in WO03068827,WO03068848 and WO2005/021612.

Practical Applications

The polymers of use according to the invention can be employed invirtually all of the fluids used in oil extraction and potentiallysubject to the loss of fluid.

According to one embodiment, the fluid (F) comprises solid particles (p)and/or is brought into contact with solid particles (p) within thesubterranean formation subsequent to its injection.

According to another embodiment, the fluid (F) injected under pressureinto a subterranean formation does not comprise solid particles (p).

According to a specific embodiment of the invention, the fluid (F) is anoil cement grout which comprises the polymer (P) as additive. In thiscase, the polymer (P), in combination with the particles present in thecement, provides the effect of control of fluid loss during thecementing.

According to another embodiment, the fluid (F) is a drilling fluid or afracturing fluid which comprises the polymer (P) in combination withparticles (p). The particles (p) are then generally introduced jointlywith the polymer into the fluid (F) before the injection of the fluid.The polymer then generally provides stabilization of the dispersion ofthe particles in the fluid (F) by keeping at least a portion of theparticles (p) in suspension in the fluid.

The concentrations of polymer and particles to be employed in thesevarious fluids can be adjusted individually as a function of theapplication targeted and of the rheology desired.

Various aspects and advantages of the invention will be furtherillustrated by the examples below. Examples B to D illustrate theinvention.

EXAMPLES Example A Poly(Dimethylacrylamide/AMPS) 60/40 Mol % Mw=2000kg/mol (SEC-MALS Characterization) (Comparative Example)

7.37 g of mercaptoacetic acid (1% by weight aqueous solution), 39.34 gof dimethylacrylamide (DMAm), 121.30 g of2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS) (50% byweight aqueous solution) and 820.57 g of demineralized water wereweighed into a 1000 ml flask. The solution was stirred for 2 min using amagnetic bar and then the pH was adjusted to 7.6 using a 20% sodiumhydroxide solution.

This solution was charged to a 2 l glass reactor equipped with an anchorstirrer, with a nitrogen inlet, with a temperature probe and with areflux condenser. Degassing by bubbling was carried out for 1 h and thesolution was heated to 62° C. When the temperature was stable, 3.2 g oftetraethylenepentamine (TEPA) (10% by weight aqueous solution) wereadded. After 2 min, 8.21 g of sodium formaldehyde sulfoxylate (NaFS)(30% by weight aqueous solution) were added. Stirring was allowed totake place for 1 h and then the reactor was emptied.

Example B Poly(Dimethylacrylamide/AMPS/tBS) 59.55/39.7/0.75 Mol % n_(H)20 Mnth 2 000 000 g/mol

Stage 1. Preparation of a Micellar Solution of 4-Tert-Butylstyrene (tBS)with Sodium Dodecyl Sulfate (SDS)—SOLUTION A

27 g of SDS and 103.16 g of distilled water were introduced at ambienttemperature (20° C.) into a 250 ml flask. Stirring was carried out on awater bath (35° C.) for 1 h using a magnetic bar, until a clear micellarsolution was obtained. 4.84 g of tBS were then added. The mixture wasstirred on the water bath (35° C.) for 1 h, until a clear micellarsolution was obtained.

Stage 2. Micellar Polymerization

210.8 g of dimethylacrylamide, 649.9 g of2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS) (50% byweight aqueous solution), 788 g of distilled water, 118.7 g of solutionA and 5.572 g of O-ethyl S-(1-(methoxycarbonyl)ethyl) xanthate offormula (CH₃CH(CO₂CH₃))S(C═S)OEt (1% by weight solution in ethanol) wereintroduced, at ambient temperature (20° C.), into a 2500 ml flask. ThepH of the mixture was subsequently adjusted to 6 using a sulfuric acidsolution (10% by weight aqueous solution).

The mixture was introduced into a 3 l Dewar flask equipped with a lid,with an anchor stirrer, with a temperature probe and with a nitrogeninlet. The solution was degassed by bubbling with nitrogen for 1 h. 18 gof sodium formaldehyde sulfoxylate (NaFS), in the form of a 1% by weightaqueous solution, were added to the medium all at once. After 5 minutes,9 g of potassium sulfate (KPS), in the form of a 5% aqueous solution,were added all at once. This KPS solution was degassed beforehand bybubbling with nitrogen for 30 minutes.

The polymerization reaction was then allowed to take place, withstirring, at up to 40° C., for 24 h. The mixture in the Dewar flask,returned to 25° C., was discharged.

Example C Poly(dimethylacrylamide/acrylamide/AMPS/tBS)39.7/39.7/19.85/0.75 mol % n_(H) 20 Mnth 2 000 000 g/mol

Stage 1. Preparation of a Micellar Solution of 4-Tert-Butylstyrene (tBS)with Sodium Dodecyl Sulfate (SDS)—SOLUTION A

40 g of SDS and 152.82 g of distilled water were introduced at ambienttemperature (20° C.) into a 250 ml flask. Stirring was carried out on awater bath (35° C.) for 1 h using a magnetic bar, until a clear micellarsolution was obtained. 7.18 g of tBS were then added. The mixture wasstirred on the water bath (35° C.) for 1 h, until a clear micellarsolution was obtained.

Stage 2. Micellar Polymerization

266.7 g of acrylamide (50% by weight aqueous solution), 430.1 g of2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS) (50% byweight aqueous solution), 186 g of dimethylacrylamide, 726.5 g ofdistilled water, 157.1 g of solution A and 5.557 g of O-ethylS-(1-(methoxycarbonyl)ethyl) xanthate of formula(CH₃CH(CO₂CH₃))S(C═S)OEt (1% by weight solution in ethanol) wereintroduced, at ambient temperature (20° C.), into a 2500 ml flask. ThepH of the mixture was subsequently adjusted to 6 using a sulfuric acidsolution (10% by weight aqueous solution).

The mixture was introduced into a 3 l Dewar flask equipped with a lid,with an anchor stirrer, with a temperature probe and with a nitrogeninlet. The solution was degassed by bubbling with nitrogen for 1 h. 18 gof sodium formaldehyde sulfoxylate (NaFS), in the form of a 1% by weightaqueous solution, were added to the medium all at once. After 5 minutes,9 g of potassium sulfate (KPS), in the form of a 5% aqueous solution,were added all at once. This KPS solution was degassed beforehand bybubbling with nitrogen for 30 minutes.

The polymerization reaction was then allowed to take place, withstirring, at up to 40° C., for 24 h. The mixture in the Dewar flask,returned to 25° C., was discharged.

Example D Poly(acrylamide/AMPS/LMAm) 79.4/19.8/0.8 mol % n_(H) 12 Mnth 2000 000 g/mol

Stage 1. Preparation of a Micellar Solution of Laurylmethacrylamide(LMAm) with Sodium Dodecyl Sulfate (SDS)—SOLUTION A

66 g of SDS and 222.76 g of distilled water were introduced at ambienttemperature (20° C.) into a 500 ml flask. Stirring was carried out on awater bath (35° C.) for 1 h using a magnetic bar, until a clear micellarsolution was obtained. 11.24 g of LMAm were then added. The mixture wasstirred on the water bath (35° C.) for 2 h, until a clear micellarsolution was obtained.

Stage 2. Micellar Polymerization

586.4 g of acrylamide (50% by weight aqueous solution), 472.7 g of2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS) (50% byweight aqueous solution), 429.9 g of distilled water, 279.1 g ofsolution A and 5.507 g of O-ethyl S-(1-(methoxycarbonyl)ethyl) xanthateof formula (CH₃CH(CO₂CH₃))S(C═S)OEt (1% by weight solution in ethanol)were introduced, at ambient temperature (20° C.), into a 2500 ml flask.The pH of the mixture was subsequently adjusted to 6 using a sulfuricacid solution (10% by weight aqueous solution).

The mixture was introduced into a 3 l Dewar flask equipped with a lid,with an anchor stirrer, with a temperature probe and with a nitrogeninlet. The solution was degassed by bubbling with nitrogen for 1 h. 17.5g of sodium formaldehyde sulfoxylate (NaFS), in the form of a 1% byweight aqueous solution, were added to the medium all at once. After 5minutes, 8.89 g of potassium sulfate (KPS), in the form of a 5% aqueoussolution, were added all at once. This KPS solution was degassedbeforehand by bubbling with nitrogen for 30 minutes.

The polymerization reaction was then allowed to take place, withstirring, at up to 40° C., for 24 h. The mixture in the Dewar flask,returned to 25° C., was discharged.

Evaluation of the Associative Polymers in Cement Grouts

The non-associative control polymer described in example A and also theassociative polymers resulting from examples B and C are used to preparelow-density 11.5 ppg (1 ppg=0.1205 kg/I) oil cement grouts having thefollowing formulation:

-   -   Municipal water: 477 g    -   Polymer as gel (comprising 30% of active principle): 5.3 g    -   Organic antifoaming agent: 1 g    -   Dykheroff black label cement (API Class G): 321.5 g

The fluid loss control agent is mixed with the liquid additives and withthe municipal water before incorporation of the cement.

The formulation and the filtration test were carried out according tothe standard of the American Petroleum Institute (API recommendedpractice for testing well cements, 10B, 2nd edition, April 2013).

After mixing and dispersing all the constituents of the formulation, thegrout obtained was conditioned at 88° C. for 20 minutes in anatmospheric consistometer (model 1250 supplied by Chandler EngineeringInc.), prestabilized at this temperature, which makes it possible tosimulate the conditions experienced by the cement grout during descentin a well.

The rheology of the cement grouts is subsequently evaluated using aChandler rotary viscometer (Chan 35 model) at the conditioningtemperature of the cement slag. The viscosity is measured as a functionof the shear gradient and the rheological profile of the cement slag isinterpreted by regarding it as being a Bingham fluid. The characteristicquantities extracted are thus the plastic viscosity (PV, expressed inmPa·s) and the yield point (yield stress, expressed in lb/100 ft²). Thefluid loss control performance was determined by a static filtration at88° C. in a double-ended cell with a capacity of 175 ml equipped with325 mesh×60 mesh metal screens (supplied by Ofite Inc., reference170-45). The performances of the polymers in the cement formulations aregiven in table 4 below:

TABLE 4 performances FL API vol PV Reference (ml) (mPa · s) A 260 6(calculated) B 120 22 C 110 24 D  88 21

The fluid loss volume is calculated when the test cannot be carried outfor 30 min and when passage of the nitrogen (percolation through thefiltration cell) is observed. In this instance, the comparative exampleA cannot provide correct control of fluid loss and the nitrogenpercolates at t=20 min. In the case of the polymers B, C and D accordingto the invention, the nitrogen does not percolate during the 30 min ofthe test and the fluid loss volume remains low, at around 100 ml.

Evaluation of the Associative Polymers as Fracturing Fluid or ReservoirDrilling (Drill-In) Fluid

The polymer of example D is dispersed at 0.5% by weight in a 2% KClsolution. The fluid, once homogenized, is filtered against a ceramicfilter with a permeability of 400 mD (supplied by Ofite, model 170-55).The filtration is carried out for 30 min under a pressure of 35 bar at atemperature of 88° C.

The amount of fluid collected after 30 min is 30 ml. In the absence offiltration control, a volume of the order of 100 ml is expected in lessthan 1 min.

The invention claimed is:
 1. A process for controlling fluid loss in afluid (F) injected under pressure into a subterranean formation, theprocess comprising forming fluid (F) with solid particles (p) insuspension and amphiphilic sequential copolymers (P) comprising: atleast one chain (C) soluble in the fluid (F) comprising hydrophilic andhydrophobic units, wherein the chain (C) is obtained by micellarpolymerization; and at least one block (B) insoluble in the fluid (F);and injecting the fluid (F) under pressure into the subterraneanformation, thereby controlling fluid loss in the fluid (F) where thefluid (F) which comprises the copolymers (P) as additive also comprisescement particles as the solid particles (p).
 2. The process according toclaim 1, wherein chain (C) is obtained by a process comprising a stage(e) of micellar radical polymerization in which the following arebrought into contact, within an aqueous medium (M): hydrophilicmonomers, dissolved or dispersed in said aqueous medium (M); hydrophobicmonomers in the form of a micellar solution, namely a solutioncontaining, in the dispersed state within said aqueous medium (M),micelles comprising these hydrophobic monomers; and at least one radicalpolymerization initiator.
 3. The process according to claim 1, whereinchain (C) is obtained by a process comprising a stage (E) of micellarradical polymerization in which the following are brought into contact,within an aqueous medium (M): hydrophilic monomers, dissolved ordispersed in said aqueous medium (M); hydrophobic monomers in the formof a micellar solution, namely a solution containing, in the dispersedstate within said aqueous medium (M), micelles comprising thesehydrophobic monomers; at least one radical polymerization initiator; andat least one radical polymerization control agent.
 4. The processaccording to claim 3, wherein the radical polymerization control agentis a compound which comprises a thiocarbonylthio—S(C═S)—group.
 5. Theprocess according to claim 1, wherein the fluid (F) is an aqueous fluid.6. The process according to claim 2, wherein said aqueous medium (M) iswater or a water/alcohol mixture.
 7. The process according to claim 2,wherein the dispersed state is obtained using at least one surfactant.8. The process according to claim 2, wherein the at least one radicalpolymerization initiator is water-soluble or water-dispersible.
 9. Theprocess according to claim 3, wherein said aqueous medium (M) is wateror a water/alcohol mixture.
 10. The process according to claim 3,wherein the dispersed state is obtained using at least one surfactant.11. The process according to claim 3, wherein the at least one radicalpolymerization initiator is water-soluble or water-dispersible.
 12. Theprocess according to claim 4, wherein the radical polymerization controlagent is a xanthate.